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New insights on ChlD1 function in Photosystem II from site-directed mutants of D1/T179 in Thermosynechococcus elongatus
摘要： The monomeric chlorophyll, ChlD1, which is located between the PD1PD2 chlorophyll pair and the pheophytin, PheoD1, is the longest wavelength chlorophyll in the heart of Photosystem II and is thought to be the primary electron donor. Its central Mg2+ is liganded to a water molecule that is H-bonded to D1/T179. Here, two site-directed mutants, D1/T179H and D1/T179V, were made in the thermophilic cyanobacterium, Thermosynechococcus elongatus, and characterized by a range of biophysical techniques. The Mn4CaO5 cluster in the water-splitting site is fully active in both mutants. Changes in thermoluminescence indicate that i) radiative recombination occurs via the repopulation of *ChlD1 itself; ii) non-radiative charge recombination reactions appeared to be faster in the T179H-PSII; and iii) the properties of PD1PD2 were unaffected by this mutation, and consequently iv) the immediate precursor state of the radiative excited state is the ChlD1+PheoD1? radical pair. Chlorophyll bleaching due to high intensity illumination correlated with the amount of 1O2 generated. Comparison of the bleaching spectra with the electrochromic shifts attributed to ChlD1 upon QA? formation, indicates that in the T179H-PSII and in the WT*3-PSII, the ChlD1 itself is the chlorophyll that is first damaged by 1O2, whereas in the T179V-PSII a more red chlorophyll is damaged, the identity of which is discussed. Thus, ChlD1 appears to be one of the primary damage site in recombination-mediated photoinhibition. Finally, changes in the absorption of ChlD1 very likely contribute to the well-known electrochromic shifts observed at ~430 nm during the S-state cycle.
关键词： ChlD1,Electrochromic shifts,P680,Photosystem II,Reaction center
更新于2025-11-14 15:14:40
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Electronic Structure of Chlorophyll a Solution Investigated by Photoelectron Yield Spectroscopy
摘要： Various bio-related processes are driven by electron transfer reactions. Therefore the electronic structures of bio-molecules in their living environment are keys of their functionalities. One significant example photosynthesis which has attracted much attention due to urgent necessity of clean energy source. In this study, we carried out photoelectron yield spectroscopy (PYS) measurements to demonstrate the electronic structures of oligomerizedChl-a molecules, which is known as an essential reaction center of the photosystem in general green plants, under the atmospheric environment. The ionization energies of the Chl-a aggregates are successfully derived.
关键词： Photoelectron Yield Spectroscopy,Polarization energy,Light harvesting antenna,Photosynthesis,Photosystem,Electronic structure,Ionization energy,Reaction center,Chlorophyll a
更新于2025-09-23 15:23:52
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Assignment of NMR resonances of protons covalently bound to photochemically active cofactors in photosynthetic reaction centers by 13C–1H photo-CIDNP MAS-J-HMQC experiment
摘要： Modified versions of through-bond heteronuclear correlation (HETCOR) experiments are presented to take advantage of the light-induced hyperpolarization that occurs on 13C nuclei due to the solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) effect. Such 13C–1H photo-CIDNP MAS-J-HMQC and photo-CIDNP MAS-J-HSQC experiments are applied to acquire the 2D 13C–1H correlation spectra of selectively 13C-labeled photochemically active cofactors in the frozen quinone-blocked photosynthetic reaction center (RC) of the purple bacterium Rhodobacter (R.) sphaeroides wild-type (WT). Resulting spectra contain no correlation peaks arising from the protein backbone, which greatly simplifies the assignment of aliphatic region. Based on the photo-CIDNP MAS-J-HMQC NMR experiment, we obtained assignment of selective 1H NMR resonances of the cofactors involved in the electron transfer process in the RC and compared them with values theoretically predicted by density functional theory (DFT) calculation as well as with the chemical shifts obtained from monomeric cofactors in the solution. We also compared proton chemical shifts obtained by photo-CIDNP MAS-J-HMQC experiment under continuous illumination with the ones obtained in dark by classical cross-polarization (CP) HETCOR. We expect that the proposed approach will become a method of choice for obtaining 1H chemical shift maps of the active cofactors in photosynthetic RCs and will aid the interpretation of heteronuclear spin-torch experiments.
关键词： MAS-J-HSQC,Solid-state photo-CIDNP,HETCOR,MAS-J-HMQC,Bacterial reaction center
更新于2025-09-23 15:23:52
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Theoretical Model of Exciton States and Ultra-fast Energy Transfer in Heliobacterial Type-I Homodimeric Reaction Center
摘要： A simple theoretical model of exciton dynamics was proposed to interpret the fast excitation energy transfer process in the Type-I homodimeric reaction center of Heliobacterium modesticaldum (hRC); this structure was recently identified and shown to resemble that of the plant/cyanobacterial photosystem I (PSI) reaction center. The exciton state model, which mainly relies on the geometries of 54 bacteriochlorophyll (BChl) g, 4 BChl-g′ and 2 chlorophyll (Chl) a on hRC and assumes constant site energy values for the pigments, reproduced the absorption spectrum of hRC rather well. The model also enabled numerical analysis of the exciton dynamics on hRC, which can be compared with the decay-associated spectra obtained by the laser spectroscopy experiments. The model indicates that the stronger transition-dipole moment on BChl-g contributes to the faster energy transfer due to the higher coherency of the delocalized exciton states on hRC compared to that on PSI that arranges Chl-a at almost homologous locations.
关键词： chlorophyll,photosystem I,bacteriochlorophyll,exciton dynamics,energy transfer,reaction center
更新于2025-09-23 15:21:21
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ROLE OF CYCLIC AND PSEUDO-CYCLIC ELECTRON TRANSPORT IN RESPONSE TO DYNAMIC LIGHT CHANGES IN PHYSCOMITRELLA PATENS
摘要： Photosynthetic organisms support cell metabolism by harvesting sunlight and driving the electron transport chain at the level of thylakoid membranes. Excitation energy and electron flow in the photosynthetic apparatus is continuously modulated in response to dynamic environmental conditions. Alternative electron flow around photosystem I plays a seminal role in this regulation contributing to photo-protection by mitigating over-reduction of the electron carriers. Different pathways of alternative electron flow coexist in the moss Physcomitrella patens, including cyclic electron flow mediated by the PGRL1/PGR5 complex and pseudo-cyclic electron flow mediated by the flavodiiron proteins FLV. In this work we generated P. patens plants carrying both pgrl1 and flva knock-out (KO) mutations. A comparative analysis of the WT, pgrl1, flva and pgrl1 flva lines suggests that cyclic and pseudo-cyclic processes have a synergic role in the regulation of photosynthetic electron transport. However, while both contribute to photosystem I protection from over-reduction by modulating electron flow following changes in environmental conditions, FLV activity is particularly relevant in the first seconds after a light change while PGRL1 has a major role upon sustained strong illumination.
关键词： Photosynthetic Reaction Center Complex Proteins,Photosynthesis,photoprotection,Energy metabolism,Evolution, Molecular,Bryophyta
更新于2025-09-10 09:29:36